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Insight into hexanuclear peroxotantalum complexes: synthesis, characterization, and efficient catalyst for amidation reaction

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Abstract

Polyoxometalates (POMs), large oxoanions of the group 5 and 6 elements, attract attention due to their use as oxidation-stable catalysts and ligands. Different from the well-known V, Mo, and W POMs, the group V POMs of Ta assemble and are stable only in highly alkaline solution rather than acidic solution. In this paper, we successfully synthesized and structurally characterized two unprecedented peroxotantalum-containing clusters, KNa2[HSe2(TaO2)6(OH)4(H2O)2O13]·15H2O (1) and Cs2K1.5Na1.5[Se4(TaO2)6 (OH)3O18]·17H2O (2), which comprises a 6-peroxo-6-tantalum core stabilized by two and four selenite centers, respectively. The simple, one-pot synthesis of 1 and 2 involving addition of sodium selenite into the acidified hexatantalate aqueous solution in the presence of hydrogen peroxide could represent a general procedure for incorporating heteroatoms into peroxo-polyoxotantalate species, thus opening new possibilities for this emergent branch of polyoxotantalate chemistry. Moreover, the catalytic properties of these two compounds were investigated using succinic anhydride and phenylamine as the model substrate, and compound 2 presents excellent catalytic activity in the amidation reactions of anhydrides and amines.

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Acknowledgements

This study was financially supported by the National Natural Science Foundation of China (Grant Nos. 21671056 and 22071045), the Program for Science & Technology Innovation Talents in Universities of Henan Province (Grant No. 19HASTIT044), and Excellent Youth Science Fund Project of Henan Province (Grant No. 202300410042).

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Authors and Affiliations

  1. Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, 475004, China

    Wei-**n Du, Meng-Yuan Cheng, Ya-Chun Ma, **g-Wen Shi & Dong-Di Zhang

  2. Jiangxi Province Key Laboratory of Synthetic Chemistry, Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation, East China University of Technology, Nanchang, 330013, China

    Ke Li

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Wei-**n Du, Ke Li and Dong-Di Zhang wrote the draft; Meng-Yuan Cheng, Ya-Chun Ma, **g-Wen Shi and Ke Li collected the data; Ke Li and Dong-Di Zhang contributed to conceived the idea of the study. All authors contributed to the writing and revisions.

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Du, WX., Cheng, MY., Li, K. et al. Insight into hexanuclear peroxotantalum complexes: synthesis, characterization, and efficient catalyst for amidation reaction. Tungsten 4, 158–167 (2022). https://doi.org/10.1007/s42864-021-00114-5

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